ENAS 606: Polymer Physics, Problem Set 1

January 29th, 2009

Solutions are due at the start of class on Thur 2/12

1.

[15 pts] This question involves use of MATLAB to generate trajectories for random walks in three-dimensions.
Generate ensembles of at least 1000 trajectories for an ideal random walk and a self-avoiding random walk (monomers cannot revisit an occupied point in space) on a cubic lattice. Make calculations for N=100, 500, 1000, 5000 and 10000 monomers or steps. The chain is allowed to take steps of unit length in any of the x, y or z directions. (a) Provide a plot and show how R2 scales with N in each case. Recall that
N N

R2 =
i=1 j=1

(Ri .Rj )

(b) What is the probability distribution function P (R) for N=10000?

2 2 (c) Calculate the radius of gyration, Rg and show how it varies with N . How does R2 / Rg vary with N ? Recall that N 2 Rg = 1/N 2 i=1

(Ri Rj )2

(d) Subdivide your ideal random walk N = 10000 chain by considering only every nth monomer where n = 2, 4, 8, 32 and 128. Are the reduced trajectories still Gaussian in their statistics? At what n do they deviate? 2.

[20 pts]
Consider the pairwise interaction between uncharged colloidal particles, mediated by a polymer chain attached at their surfaces along a line joining their centers. We examine a linear arrangement of three such particles, as shown in Figure 1. The attractive interaction between spherical particles due to Van der Waals forces is written as (s) = A/6 2R2 2R2 + 2 + ln + 4Rs s + 4Rs + 4R2 s2 + 4Rs + 4Rs + 4R2

s2

s2

Figure 1: Colloidal particles joined by polymer chains 1

where s is the separation between the surfaces of the spheres (t 2r in Figure 1), R is the radius of the spheres and A is the Hamaker constant. A good value for the Hamaker constant is 5E 20 J or about 10 kT at room temperature. For R s, this expression reduces to (s) AR 12s

(a) Make a plot of the inter-particle potential (in units of kT ) between the middle and either end particle due solely to the Van der Waals interaction, out to a center-center distance of 10r. (b) Consider the displacement of the center particle away from equilibrium (x = 0). The free energy change associated with the change in the end-end dimensions of the left and right polymers modies the interaction potential between the particles. Lets examine polymers with Rg = r, r/2 and r/100, separated by t = 4r, 8r and 16r (9 cases). i. Construct and plot the modied potentials (i.e. add the contribution from the polymer chains to the potential from part I above) under the assumption that the chains are Gaussian. That is, they follow force-displacement relationships of the form f = 3kT R 2 R0

where R0 is the unperturbed end-end distance of the chain. ii. Construct and plot the modied potentials under the assumption that the chains are worm-like. That is, they follow force-displacement relationships of the form f b 2R 1 + = kT Rmax 2 Rmax Rmax R
2

1 2

given Rmax = 50b. In the WLC model, b = 2lp and the radius of gyration is given by
2 Rg = 3 4 2lp 2lp 1 2 Rmax lp lp + 2 3 Rmax Rmax

1 exp

Rmax lp

(c) What other factors could be considered in this picture to make it more realistic? 3.

[10 pts] Problem 2.12 from the text

Consider a polymer containing N Kuhn monomers (of length b) in a dilute solution where ideal chain statistics apply. The molar mass of the polymer is M .
2 (a) What is the mean-square end-to-end distance R0 of the polymer?

(b) What is the fully extended length Rmax ?

2 (c) What is the mean-square radius of gyration Rg of this polymer?

(d) Estimate the overlap concentration c for this polymer, assuming that the pervaded volume of the chain is a sphere of radius Rg (e) How does this overlap concentration depend on the degree of polymerization (f) What is the ratio of its fully extended length to the average root mean square end-to-end distance Rmax /R0 ? (g) Consider an example of a polymer with molar mass M = 104 g/mol. consisting of N = 100 Kuhn monomers (of length b = 10 and determine R0 , Rg , Rmax , c and Rmax /R0 . A 4.

[5 pts]
The concept of the tension blob was introduced to make a simple scaling argument for the force-extension response of a Gaussian chain. Describe the concept and its utility in your own words.